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Split herbicide application: A practical approach to enhancing water quality
No full textHerbicide contamination of surface and groundwater poses a risk to water quality, particularly in regions where agricultural practices rely on herbicides to help maintain crop yields. Herbicides such as 2-methyl-4-chlorophenoxyacetic acid (MCPA; phenoxy-carboxylic acid) and clopyralid (Pyridine-carboxylic acid) are commonly used to control broadleaf weeds, and consequently they are frequently detected in European water bodies. This presents significant challenges to the achievement of “good” water quality status by European Union (EU) member states.
This study evaluated the effectiveness of a novel approach to mitigate MCPA and clopyralid losses while maintaining agricultural efficacy, namely split herbicide application. Split herbicide applications involve multiple applications of herbicides across a season that cumulatively equal the same amount applied in one maximum single dose.
The experimental approaches employed included controlled rainfall simulations and laboratory soil column trials to determine MCPA and clopyralid fate due to runoff and leaching, respectively, in agricultural soils. The results demonstrated a substantial reduction in total herbicide loss in both surface runoff and leachate, compared to conventional single-dose applications. Similarly, leaching experiments confirmed reduced herbicide mobility, particularly in organomineral soils, which exhibited enhanced adsorption capacity compared to mineral soils.
Microbial community analysis indicated a potential biological contribution to the reduction in total herbicide loss with a split application approach. Soils treated with split herbicide applications exhibited increased diversification of classes of the bacterial tfdA gene, which is involved in the degradation of MCPA. This adaptive microbial response highlights the potential for split applications to enhance natural attenuation processes, thereby reducing the environmental persistence and transport of herbicides.
The findings align with the objectives of the EU pesticide regulations, including the Water Framework Directive and Sustainable Use Directive, which aim to balance agricultural productivity with environmental sustainability. Split herbicide application offers a pragmatic solution, addressing key limitations of existing mitigation strategies such as buffer zones and precision agriculture, which often face implementation barriers due to cost or site-specific constraints.
Despite its potential, the adoption of split applications requires an in-situ study to validate its efficacy in real life situations. Further research is needed to assess long term efficacy across diverse agroecological contexts, including variations in climate, crop type, and farming practices. Additionally, integrating split herbicide applications with complementary strategies, such as biochar amendments or constructed wetlands, could be investigated to evaluate their combined effectiveness.
This thesis contributes to the scientific understanding of herbicide management by providing robust experimental evidence for the efficacy of split applications. The results support the adoption of this approach as a viable and sustainable practice for reducing herbicide contamination in surface and groundwater. By mitigating environmental risks while maintaining weed control efficiency, split herbicide applications represent a critical advancement in the pursuit of sustainable agriculture and water resource protection
Development of a novel TRPV1 dependent in vitro model of nociceptive pain
No full textThis study aims to develop of a novel in vitro model for pain research, focusing on the TRPV1 receptor, which plays a crucial role in pain mechanisms. Given the limitations of current therapies in treating pain sensation without targeting underlying causes, this research aims to advance understanding of TRPV1’s role in neuronal hyperexcitability and its potential as a therapeutic target.
The ND7/23 cell line was transfected with human TRPV1 to create a stable neuronal model that closely mimics dorsal root ganglion neurons, known for their role in pain transmission. This model allows for a detailed investigation of TRPV1’s functionality, particularly its interactions with voltage-gated ion channels, which are key in modulating neuronal excitability and pain signalling.
Capsaicin, a natural compound known for activating TRPV1, was used to evaluate the model’s effectiveness. Calcium imaging confirmed capsaicin responsiveness to TRPV1 in ND7/23-TRPV1 cells. Automated patch clamp experiments demonstrated full functionality of TRPV1 in response to heat and pH, as well as the specificity TRPV1-capsaicin binding, with the use of capsazepine. In dose response studies capsaicin demonstrated a higher potency in ND7/23-TRPV1 cells compared to CHO-TRPV1 cells, confirming its neuronal characteristics. In further studies, capsaicin highlighted its potential in modulating ionic currents and action potentials. The findings suggest that capsaicin, through TRPV1 activation, can modulate neuronal activity, offering promise as a therapeutic agent for chronic pain management.
This study establishes a robust in vitro model for pain research, offering new insights into the complex mechanisms of pain. It underscores the critical role of TRPV1 in modulating neuronal excitability, laying the foundation for the development of targeted analgesic therapies
Design and synthesis of metal organic frameworks for encapsulation of multiple anti-cancer drugs and environmental applications
No full textMetal-Organic Frameworks (MOFs) have the potential to offset some of the terrible side effects caused by the drugs currently used in cancer treatment. MOFs have high porosity, low cytotoxicity, good biocompatibility, biodegradability, and target-specific behaviour, encapsulating drugs and subsequently releasing them at tumour sites. MOFs allow for a slower release of the drugs, preventing the burst effect caused by immediate release of the drug. Although the potential of MOFs as drug carriers has been well established, their use in combinatorial treatments that involve more than one drugs has been less investigated. Dual drug encapsulation and release would improve the potency of the anti-cancer treatment because of the synergistic effect of the two drugs. Dual drug encapsulation and release can also help to overcome the multidrug resistance effect that comes from cancer cells becoming resistant to anti-cancer drugs.
With the above in mind, we decided to explore the potential of MOFs as multiple drug carriers. For this purpose, NUIG4 was used, it holds the record in doxorubicin (DOX) uptake, it is water stable and biocompatible and protects the healthy cells from the drug cytotoxicity. Herein, the capacity of NUIG4 to deliver dox or mitoxantrone (MIT) and 5-fluorouracil (5-FU) is reported. Each anti-cancer drug that are used in this project have a different mechanism of action; this can help to overcome multidrug resistance. 5-fluorouracil intercepts the replication of the cancer cells genetic material, due to the cancer cells mistaking 5-fluorouracil for uracil, while doxorubicin hydrochloride intercepts the replication process of the cancer cells by DNA intercalation, it slots itself between the base pairs of DNA. Mitoxantrone is a synthetic anti-cancer drug which is similar in structure to anthracycline drugs, such as doxorubicin. It has a similar mechanism of action to that of doxorubicin. The initial results suggest the successful encapsulation of DOX/ MIT and 5-FU, and a controlled release of the drugs, as a result of the large pore size and subsequent large internal surface area.
MOFs also have the potential to encapsulate different environmentally toxic materials. This thesis reports the capacity of NUIG4 to encapsulate Tetracycline hydrochloride (TET). TET is an antibacterial drug which is used for the treatment of animals and humans. It is dangerous for the environment; it damages microbial communities and inhibits algae growth. It is often slow to degrade and infiltrates water systems, which can increase antibiotic resistance. The removal of TET from the environment would lower antibiotic resistance and allow algae growth, preliminary results show the successful encapsulation of TET by NUIG4. The large pore size and internal surface area of NUIG4 allow for this encapsulation.
The synthesis of novel MOFs is very important as it can result in MOFs which can encapsulate more complex compounds, or it could result in new synthesis methods of MOFs. These new synthesis methods could be more environmentally friendly MOFs, though they are still capable of encapsulating a wide variety of guest molecules for many different applications. The final project covered in this thesis shows the synthesis of a novel MOF synthesised by the mechanochemical synthesis method. This method involves physical force causing chemical reactions, it is solvent free and has a high yield. It had successful encapsulation of an anti-cancer drug
A constructivist grounded theory of defending inaction in the implementation of intercultural education in post-primary schooling in Ireland: Teacher perspectives
No full textIreland has experienced considerable diversification in recent decades. In response to the increased diversity in classrooms, the Irish government has adopted a policy of intercultural education. Despite this, existing research is critical of the form of intercultural education found in Irish schools. This is broadly reflective of international research, which often finds teachers’ understandings of intercultural education to be superficial and celebratory. There is a gap in existing literature, however, on the factors that impact on how teachers understand intercultural education. This research examines Irish post-primary teachers’ understandings of intercultural education and influencing factors. In doing so, it also excavates teachers’ experiences of racism in Irish schools. As this is an under-researched, and thus under-theorised area, a Constructivist Grounded Theory (CGT) methodology was adopted for this study. CGT research aims to develop our conceptual and theoretical understanding of a substantive area, whilst ensuring such theory is rooted in the data gathered in the field. Semi-structured interviews were conducted with thirty-one post-primary teachers. Data were analysed using CGT procedures of coding and categorising, with data collection and analysis conducted iteratively over three rounds. At several points, participants were actively involved in the research process and thus the co- construction of theory.
A CGT of ‘defending inaction in the implementation of intercultural education’ was constructed, explaining how teachers value intercultural education but defend the lack of it in their schools. These defences are important for maintaining teachers’ professional identities in the face of inaction regarding intercultural education. The CGT had three sub-categories constructed as part of a three-stage process. The first of these, ‘‘‘Opening my eyes” to diversity and privilege’, explains participants’ upbringings and how encounters with ethno-cultural diversity in adulthood improved their understanding of diversity and privilege. The second sub-category, ‘Valuing diversity and intercultural education’, examines participants’ understandings intercultural. Finally, ‘Defending the lack of intercultural education’ explains how participants noted and defended the lack of intercultural education in their schools.
These findings are examined using international literature on teachers’ approaches to intercultural education. In line with existing research, participants largely held superficial and celebratory understandings of intercultural education. This study explores how participants’ experiences of ethno-cultural diversity in their personal and professional lives influenced their understandings of intercultural education. Interestingly, participants were aware of the ‘tokenistic’ nature of celebratory approaches to intercultural education and the lack of action related to intercultural education in their schools. Importantly, this study is the first to explore the ways teachers defend inaction regarding intercultural education. It uses literature on resistance to innovation and teacher professional identity to explain these defences. The findings of this study also deepen our understandings of racism in Irish schools. They excavate examples of explicit racism from teachers and explain the ways some participants in this study ‘othered’ minoritised students or avoided challenging racism from their colleagues due to a lack of professional security. These findings suggest interesting routes for further research.
The findings have implications for both educational policy and practice. These include further training for teachers in intercultural education and its inclusion in the school self-evaluation process
Magnetically tunable topological states in translational-rotational coupling metamaterials
No full textIn this work, an approach for engineering translational-rotational coupling (TRC) metamaterials with magnetically tunable topological states is proposed. The metamaterial exhibits diverse nonlinear mechanical behaviors, remotely controlled and activated by an external magnetic field. The design is realized through a multi-material microstructure with highly deformable hinge configurations, targeting desirable strain-softening/stiffening characteristics. This 3D-printable hinge design eliminates the complex manual assembly processes typically required in current TRC metamaterials that are based on triangulated cylindrical origami. The stiffness transition property of the TRC metamaterials can be exploited to break the space-inversion symmetry and thus achieve tunable topological phase transition. Specifically, hard-magnetic active material is incorporated to enable untethered shape- and property-actuation in these metamaterials. The TRC metamaterial design is supported by a simplified analytical model whose stiffness parameters are directly linked to the hinge microstructure, offering a significant improvement over previous empirical model. The accuracy of the analytical model is demonstrated through the comparison with the finite element and experimental results. Through these methods, the deformations induced by a magnetic field and the dynamics of superimposed waves in the TRC metamaterial system are studied. Thanks to the magneto-mechanical coupling effect, the proposed TRC metamaterial design enables remote tunability of wave dispersions and topological invariants (including the Zak phase and winding number), in contrast to existing designs that require direct mechanical loading to achieve similar effects. This tunability extends to the control of topologically protected edge and interface states within the finite system. Our findings can potentially open new ways for designing remotely reconfigurable and switchable soft mechanical metamaterials with robust wave guiding and energy harvesting capabilities.QZ thanks the support of the European Union's (EU) Horizon Europe research and innovation funding program through the Marie Skłodowska-Curie Actions (Grant No. 101106301-MetaMagic). SR thanks for the support of the European Research Council (ERC) through Grant No. 852281-MAGIC.peer-reviewe
Motion tracking analysis in elite soccer: Pattern discovery
No full textIn modern soccer (football), extensive motion tracking data are collected, capturing players’ movements at a rate of 25 times per second. Traditionally, these data have been utilised for tactical analysis, focusing on aspects such as team formation and identifying motion patterns. However, my research aims to leverage these data in a novel manner, prioritising player performance, injury management, rehabilitation, and player welfare. This thesis seeks to develop new statistical methods to identify personalised patterns of movement, enabling the creation of tailored training sessions that address the physiological demands specific to each player’s position. Additionally, by analysing the types of movements and associated physical forces, sports scientists can design rehabilitation programs for injured players more effectively. To this end, advanced modelling techniques are incorporated to enhance the analysis of motion tracking data. The bivariate generalised linear model (GLM) offers a sophisticated approach to jointly modeling angular change and speed change in player trajectories. By characterising trajectories into interpretable parameters, such as angular change and speed change, this model provides valuable insights into the underlying patterns of player movement. Furthermore, the bivariate GLM facilitates the clustering of trajectories based on the estimated parameters, allowing for the identification of similar movement patterns among players.IRC & Orreco LT
Understanding endothelial colony forming cell biology in health and diabetes mellitus
No full textEndothelial colony-forming cells (ECFCs) are progenitors of endothelial cells with significant proliferative and angiogenic ability, making them a promising therapeutic option for diseases like ischemic heart disease and peripheral artery disease. However, their clinical application is hindered by several barriers, including heterogeneity among donors, tissue sources, and cell subpopulations, as well as dysfunctional phenotypes observed in disease states such as diabetes mellitus (DM). Therefore, it is important to understand their characteristics and heterogeneity in health and disease states, and elucidate the underlying mechanisms of ECFC dysfunction to enable the clinical application of ECFCs.
Transcriptomic analysis is a powerful tool for exploring the key molecules and pathways involved in health and disease and can be used to understand the characteristics and heterogeneity of ECFCs. In Chapter 3, we analyzed the public single-cell RNA sequencing (scRNA-seq) and bulk RNA-sequencing datasets of healthy ECFCs. Compared with human umbilical vein endothelial cells (HUVECs), cord blood ECFCs (CB-ECFCs) and peripheral blood ECFCs (PB-ECFCs) had higher VEGFR2 expression levels. Moreover, CB-ECFCs could be divided into seven subtypes with distinct gene expression profiles and metabolic activities. TGFB1 and COL1A1 could serve as potential markers to identify the ECFC subtypes with reduced angiogenesis ability. In Chapter 4, we compared the gene expression pattern between control and diabetic PB-ECFCs using bulk RNA-sequencing, identifying that TNF-α pathway was activated in diabetic ECFCs. This suggests that an inflammatory environment may contribute to ECFC dysfunction in DM. Lastly, in Chapter 5, TNF-α was used to mimic the inflammatory environment of DM. Our data revealed that TNF-α treatment inhibited the proliferation, tube formation but increased THP-1 cell adhesion in PB-ECFCs. Three miRNAs (miR-146a-5p, miR-199a-3p, and miR-199a-3p) were upregulated in PB-ECFCs after TNF-α treatment. The overexpression of miR-146a-5p were able to rescue the inflammatory effects induced by TNF-α. Collectively, the data presented in this thesis revealed the characteristics of ECFCs in health and DM and highlighted the protective role of miR-146a-5p against inflammation, which could help to improve the therapeutic efficacy of diabetic ECFCs
Where next for carbon literacy? Tackling climate misinformation and addressing climate (in)justice
No full textTackling the climate crisis requires widespread awareness of the urgency and the scale of the climate challenge as well as greater understanding of climate mitigation actions and how everyday activities contribute to greenhouse gas emissions. Carbon literacy research and practice aims to address these information needs and related skills deficits through communication campaigns to motivate and mobilise carbon reduction activities by individuals, communities, and organisations. However, carbon literacy is also a dynamic concept shaped by policies and technologies. As a result, there is a need for ongoing development in this evolving domain of climate communications.
This chapter reviews developments in carbon literacy campaigns focusing on the UK. This reveals a shift from addressing knowledge and skills deficits to the more recent focus on specific mitigation actions, as well as new communications approaches drawing on storytelling and experiential engagement. It then highlights two contemporary challenges for climate action communication: the proliferation of climate misinformation, as well as growing concerns about the fairness of decarbonisation processes and the need for a “just transition.” It argues that in the context of a climate crisis, carbon literacy research and practice must take these developments in public discourse into account and engage with climate misinformation and climate justice studies.peer-reviewe
N-terminal protein recognition by supramolecular synthons
No full textThis research investigate the biomolecular recognition capabilities of WPCTX, an anionic phosphocavitand. Cocrystallization trials of WPCTX and two different model proteins were performed. X-ray crystallography was used to elucidate the structures of the resulting crystals. NMR spectroscopy was used to characterize the protein – macrocycle interactions in solution. WPCTX bound arginine residues in lysozyme in a trigonal cocrystal form. Three related cocrystal forms of RSL – WPCTX revealed N-terminal binding across a variety of crystallization conditions. MK-RSL, a mutant of RSL containing an extended N-terminus with a Met-Lys motif showed further N-terminal binding with WPCTX. The macrocycle in RSL and MK-RSL cocrystals, formed clusters that mediated protein assembly. These results identify a synthetic ligand capable of N-terminal recognition as well as self-assembly (cluster formation) furthering our knowledge as to how supramolecular synthons may aid protein assembly
Elucidating the drivers of butyric acid degradation and production in anaerobic digestion systems
No full textButyric acid is a highly valuable chemical due to its wide range of applications. Its production and recovery from organic waste offers greater economic benefits and reduced environmental impacts, as it is currently mainly derived from fossil fuels. Although the accumulation of butyrate is a recurrent phenomenon in anaerobic digestion, there has been limited research on the optimal conditions for butyrate accumulation and the underlying accumulation mechanisms. This thesis aimed to investigate the factors influencing butyric acid degradation and production, with the goal of identifying the optimal conditions for its accumulation in anaerobic digestion systems. The specific objectives of this PhD research were: 1) to elucidate the effects of ammonia (TAN) concentration and pH on butyrate degradation; 2) to investigate the influence of butyrate concentration and temperature on butyrate degradation and its associated metabolic pathway; 3) to identify the best conditions (pH, temperature, and inoculum to substrate ratio) for maximizing butyric acid yields and to explore the underlying mechanisms governing volatile fatty acid (VFA) distribution under varying conditions.
The results showed that at pH 7.5, butyrate degradation experienced remarkable inhibition when TAN exceeded 8.0 g N/L, while no discernible impacts were observed at pH 7.0–8.0 and 4.0 g TAN/L. Additionally, the lag phase for butyrate degradation extended with increasing TAN concentration. NH4+ contributed more to inhibition than NH3 at TAN concentrations of 2.0–20.0 g N/L. Notably, the activity of butyrate-degrading bacteria was able to be fully recovered from severe ammonia inhibition (TAN of 20 g N/L or NH3 of 779.2 mg N/L), provided a prolonged adaption time.
Complete butyrate degradation occurred in the range of 2.0 to 20.0 g COD/L, regardless of temperature (37 oC or 55 oC); however, degradation kinetics differed in the two temperature conditions. At 37 oC, iso-butyrate production was observed with butyrate concentrations from 2.0 to 20.0 g COD/L, while it only occurred with 20 g COD/L butyrate at 55 oC. The kinetic analysis of butyrate oxidation showed that the production of iso-butyrate was important for butyrate degradation. Metagenomic analysis revealed that the key enzymes such as enoyl-CoA hydratase (EC 4.2.1.17) and 3-hydroxyacyl-CoA dehydrogenase (EC 1.1.1.35) involved in iso-butyrate metabolism correlated positively with efficient butyrate degradation.
The optimal condition for efficient butyrate accumulation from glucose was pH 5.5, a temperature of 37°C, and an ISR of 1:3. Different experimental conditions significantly shaped the microbial community dynamics. The genera playing significant roles in butyrate production included Clostridium, Caproicibacter, Caproicibacterium, Sporolactobacillus, and Ethanoligenens. The relative abundance of genes encoding key enzymes involved in reverse β-oxidation significantly increased under optimal conditions, suggesting that the enhancement of butyrate production was driven by carbon chain elongation, using intermediate metabolites like ethanol or lactate as electron donors and acetate as the electron acceptor. These findings demonstrate that chain elongation can be sustained without the need for external electron donors or additional chemicals, effectively promoting both the yield and purity of butyrate.
This PhD research provides deeper insights into the biochemical and microbial mechanisms of butyrate accumulation in anaerobic digestion, and provides practical solutions for enhancing butyrate production from wastes, thereby supporting sustainable resource recovery and advancing biorefinery technologies